Ionic compounds with delocalized anionic charge, and their use as ion conducting components or as catalysts

ABSTRACT

The invention relates to an ionic compound corresponding to the formula [R 1 X 1 (Z 1 )-Q − -X 2 (Z 2 )-R 2 ] m  M m+  in which M m+  is a cation of valency m, each of the groups X i  is S=Z 3 , S=Z 4 , P—R 3  or P—R 4 ; Q is N, CR 5 , CCN or CSO 2 R 5 , each of the groups Z i  is ═O, ═NC≡N, ═C(C≡N) 2 , ═NS (=Z) 2 R 6  or ═C[S(=Z) 2 R 6 ] 2 , each of the groups R i , is Y, YO—, YS—, Y 2 N— or F, Y represents a monovalent organic radical or alternatively Y is a repeating unit of a polymeric frame.  
     The compounds are useful for producing ion conducting materials or electrolytes, as catalysts and for doping polymers.

[0001] The present invention relates to ionic compounds comprising ahighly delocalized anionic charge, to a process for their preparationand to their uses.

[0002] It is well known that the salts of strong acids such as HClO₄,HBF₄, HPF₆ and HR_(F)SO₃ (R_(F)=perfluororadical) have properties in thefield of electrochemistry and catalysis, but these properties arelimited. The “superacids” obtained by adding a Lewis acid such as SbF₅to the abovementioned compounds are moreover known. However, thesecompounds are not stable other than in protonated form and innon-solvating media such as aliphatic hydrocarbons. The salts areunstable in the usual polar solvents.

[0003] Perfluorosulfonimide derivatives H[R_(F)SO₂NSO₂R_(F)](R_(F)=perfluoroalkyl) have been studied since quite recently. They haveadvantageous stability properties in protonated form or in the form ofsalts and are used as solutes in electrochemistry and as catalysts.However, it is not possible to give these salts all of the propertiesrequired for all the applications, in particular in terms of acidity,dissociation or solubility, since the use of compounds containingperfluoro chains of several carbons only slightly increases the acidityor the dissociation of the salts, when compared with the simplestcompound R_(F)=CF₃, and induces rigidity in the molecule to thedetriment of the conductivity properties. Long fluoro chains are bothhydrophobic and oleophobic and do not allow any appreciable increase inthe solubility in organic media. Replacement of the groups R_(F) in thesimple imides with non-perfluoro or only partially fluorinated groupsreduces the acidity and the solubility substantially.

[0004] The aim of the present invention is to provide novel ioniccompounds derived from perfluorosulfonimides in which the delocalizationof the anionic charge is improved, thus resulting in markedly betteracidity and dissociation than those of the known compounds, while at thesame time retaining good stability.

[0005] Accordingly, a subject of the present invention is ioniccompounds, their uses and a process for preparing them.

[0006] One compound according to the invention is an ionic compoundcorresponding to the formula

[0007] in which:

[0008] M^(m+) is a proton or a metal cation having the valency m, chosenfrom ions of alkali metals, of alkaline-earth metals, of transitionmetals or of rare-earth metals, or an organic onium cation or anorganometallic cation, 1≦m≦3;

[0009] X¹ and X², denoted below by X^(i), represent, independently ofeach other, S=Z³, S=Z⁴, P—R³ or P—R⁴;

[0010] Q represents N, CR⁵, CCN or CSO₂R⁵;

[0011] Z¹, Z², Z³ and Z⁴, denoted below by Z^(i), represent,independently of each other, ═O, ═NC≡N, ═C(C≡N)₂, ═NS(=Z)₂R⁶ or═C[S(=Z)₂R⁶]₂, Z having the same meaning as Z^(i), it being understoodthat, in a segment —X¹-Q-X²—, not more than 3 groups Z^(i) represent ═O;

[0012] R¹, R², R³, R⁴, R⁵ and R⁶, denoted below by R^(i), represent,independently of each other, Y, YO—, YS—, Y₂N— or F;

[0013] Y represents a monovalent organic radical, preferably containingfrom 1 to 16 carbon atoms, chosen from alkyl, alkenyl, oxaalkyl,oxaalkenyl, azaalkyl, azaalkenyl, aryl, alkylaryl or perfluoroalkylradicals, or from the radicals obtained from the abovementioned radicalsby substitution, in the chains and/or the aromatic part, with heteroatoms such as halogens, oxygen, nitrogen, sulfur or phosphorus; it beingunderstood that sulfur or phosphorus are present, they can optionally belinked to substituted oxygen or nitrogen atoms, or alternatively Y is arepeating unit of a polymeric frame.

[0014] When M^(m+) is a metal cation, it can be an alkali metal (inparticular Li⁺ and K⁺), an alkaline-earth metal (in particular Mg⁺⁺,Ca⁺⁺ or Ba⁺⁺), a transition metal (in particular Cu⁺⁺, Zn⁺⁺ or Fe⁺⁺) ora rare-earth metal (in particular Re⁺⁺⁺).

[0015] When M^(m+) is an onium cation, it can be chosen from ammoniumions [N(Y^(j))₄]⁺, amidinium ions RC[N(Y^(j))₂]⁺, guanidinium ionsC[N(Y^(j))₂]₃ ⁺, pyridinium ions C₅[N(Y^(j))₆]⁺, imidazolium ionsC₃N₂(Y^(j))₄ ⁺, imidazolinium ions C₃N₂(Y^(j))₇ ⁺, triazolium ionsC₂N₃(Y^(j))₄ ⁺, carbonium ions C₆(Y^(j))₅C⁺, NO⁺ (nitrosyl) or NO₂ ⁺ions, sulfonium ions [S(Y^(j))₃]⁺, phosphonium ions [P(Y^(j))₄]⁺ andiodonium ions [I(Y^(j))₂]⁺. In the various abovementioned onium ions,the substituents Y^(j) on the same anion can be identical or different.They represent, independently of each other, H or one of thesubstituents indicated above for Y.

[0016] When M^(m+) is an organometallic cation, it can be chosen frommetalloceniums. For example, mention may be made of the cations derivedfrom ferrocene, from titanocene, from zirconocene, from an indocenium orfrom an arene metallocenium. It can also be chosen from metal cationscoordinated by atoms such as O, S, Se, N, P or As, borne by organicmolecules, in particular in the form of carbonyl, phosphine orporphyrine ligands optionally containing chirality. M^(m+) can also be acation derived from the alkyl groups defined for Y above and limited tothose containing from 1 to 10. carbon atoms, for example atrialkylsilyl, tetraalkylgermanyl or dialkylstannyl derivative; in thiscase, M is linked to the group [R¹—X¹(Z¹)-Q⁻-X²(Z²)-R²] via a verylabile covalent bond and the compound behaves like a salt. The cation M⁺can also be the repeating unit of a conjugate polymer in cationicoxidized form. As specific examples, mention may be made of themethylzinc, phenylmercury, trialkyltin or trialkyllead,chloro[ethylenebis(indenyl)]zirconium(IV) ortetrakis-(acetonitrile)palladium(II) cations. The organometallic cationcan form part of a polymer chain.

[0017] The compounds according to the invention in which at least one ofthe groups X^(i) represents a phosphorous group are particularlyadvantageous for the great stability of the P—N and P—C bonds and fortheir flexibility. As a result, these compounds are more soluble andhave a lower melting point than the sulfur-containing homologouscompounds. Moreover, a large number of phosphorous compounds bearing twosubstituents R are commercially available or can readily be synthesized.For example, mention may be made of the compounds

[0018] Mention may be made in particular of the phosphorous compounds inwhich Q represents N.

[0019] The compounds in which the radicals Z^(i) represent R_(F)SO₂N andthose in which the radicals R^(i) represent a perfluoro group or analkyl group are particularly advantageous, especially for the highacidity and the dissociation of the corresponding salts.

[0020] Among the compounds of the present invention corresponding toformula (I), mention may be made of those in which the groups X^(i)represent S-Z^(i), more particularly those in which Q is N, and whichcorrespond, respectively, to the formulae:

[0021] One particular family of compounds according to the inventioncorresponds to formula (VII), given that if R¹ is CF₃, R₂ is a phenyloptionally bearing a halogen or an NO₂, three substituents Z^(i)represent O and one substituent Z^(i) represents ═NSO₂CF₃, then M isother than an alkali metal cation or a proton.

[0022] Another family of compounds according to the inventioncorresponds to formula (I) in which the radicals R¹ and R² are chosen,independently of each other, from perfluoroalkyl radicals preferablycontaining from 1 to 8 carbon atoms, alkyl radicals preferablycontaining from 1 to 8 carbon atoms, alkenyl radicals preferablycontaining from 2 to 18 carbon atoms, dialkylamino radicals in which thealkyl radicals preferably contain from 1 to 18 carbon atoms, andstyrenyl radicals. For example, mention may be made of the compoundscorresponding to the following formulae, in which R_(f) represents aperfluoro radical, Q and M have the meaning given above, and Y, Y′, Y″,Y″′ and Y″″ have the meaning given above for Y:

[0023] The compounds corresponding to formula (I), in which the groupsZ^(i) are chosen from ═O, ═N—C≡N and ═C(C≡N)₂, constitute anotheradvantageous family. The presence of one or more groups ═N—C≡N or═C(C≡N)₂, makes it possible to increase the dissociation and theresistance to oxidation of the anion without substantially increasingits molar mass or its volume. For example, mention may be made of thefollowing compounds:

[0024] Mention may also be made in particular of the compoundscorresponding to the formula (IV)

[0025] in which three groups Z¹ to Z³ represent oxygen and Z⁴ represents═C[S(=Z)₂R⁶]₂. For example, mention may be made of the followingcompounds:

[0026] Mention may also be made of the compounds corresponding to theformula

[0027] in which the groups R^(i), Z^(i) and Q have the meaning givenabove, in particular compounds in which the groups Z^(i) are O, and Q isN.

[0028] Mention may also be made of the compounds of formula

[0029] in which the groups R_(f) and R′_(f) represent perfluoroalkylradicals, the groups Z^(i) and R^(i) have the meaning given above, inparticular compounds in which the groups Z^(i) are O, and R_(f) is CF₃.

[0030] In general, the replacement of the oxygen in the SO₂ end groupsof

[0031] with groups Z representing ═NSO₂R^(i) makes it possible toconstruct molecules of general formula:

[0032] The choice of the substituents R^(i) in the compounds of thepresent invention makes it possible to obtain compounds in which theanion has intrinsic chirality on a sulfur atom. Such compounds areuseful for inducing enantiomeric selectivity during the preparation ofactive organic compounds or for inducing stereoselectivity inpolymerization reactions. Among these compounds, mention may be made ofthose corresponding to one or other of the following formulae[R¹SO₂N—S★═O(R²)═NSO₂R⁶]⁻ in which R¹ is different from R⁶, or[R¹SO₂N—S★═O(R²)═N—S★═O(R⁵)═NSO₂R⁶]⁻. The compounds most particularlypreferred are those in which R¹ and R⁶ represent, independently of eachother, a radical chosen from F, CF₃, C₂F₅, C₄F₉, C₆F₁₃ and C₈F₁₇, and R²and R⁵ represent, independently of each other, an alkyl, an aryl, analkylaryl or a dialkylamino preferably containing from 1 to 20 carbonatoms. The ionic compounds of the present invention can be prepared byvarious processes.

[0033] In general, a compound corresponding to the formula

[0034] is prepared by reacting a precursor compound, noted below (Z¹,L)comprising the group Z¹ and a leaving group L, with a derivative A²Z² ofthe group Z² according to one of the following reaction schemes:

R¹—X¹(Z¹)-Q-X²(L)R²+A²Z²

[R¹—X¹(Z¹)-X²(L)(Z2)R²]⁻A⁺+LA

[0035] or

R¹—X¹(Z¹)-QA2+L-X²(Z²)R²

[R¹—X²(Z¹)-X²(L)(Z2)R²]⁺A⁻+LA

[0036] A represents an alkali metal, a proton, an amino orphosphorus-containing base, a trialkylsilyl group, a dialkylstannylgroup, MgL1, ZnL1, CdL1, Cu, Mg, Zn, Cd, Hg or a trialkylsilyl,trialkylgermanyl or trialkylstannyl group.

[0037] The leaving groups L or L1 are advantageously chosen fromhalogens, pseudohalogens including fluoro or non-fluoro sulfonates, andimidazoyl, triazolyl and benzotriazoyl radicals.

[0038] The compounds (Z¹,L) in which the leaving group is a halogen canbe prepared, for example, by the action of a halogenating agent on asalt R¹—X¹(Z¹)-Q-X²(O)(R²)⁻A⁺ or on the corresponding acid. The cation Ais preferably chosen from alkali metal cations, inorganic ammonium ionsNH₄ ⁺ or organic ammonium ions R³NH⁺ (including pyridinium) and the Ag⁺ion, which has strong affinity for Cl, Br and I.

[0039] Among the halogenating agents which are useful, mention may bemade of SF₄, trifluoro(diethylamino)sulfur IV (DAST), thionyl chloride,oxalyl chloride, oxalyl fluoride, phosphorus pentachloride, the mixturePΦ₃+CCl₄, (chloromethylene)dimethylammonium chloride[CH(Cl)═N(CH₃)₂]⁺Cl⁻ or its homologue derived fromN-methylpyrrolidinone, and 1-methyl-2-fluoropyridinium iodide. Thepreparation of a compound (Z¹,L) in which the leaving group is a halogenis illustrated schematically by the following example:

[CF₃SO₂NSO₂(C₄H₉)]Na+(COCl)

CO+CO₂+[CF₃SO₂NSO(C₄H₉)Cl]+NaCl

[0040] The precursor compounds (Z¹,L), in which the leaving group isimidazolyl, triazolyl or benzotriazolyl, can be obtained by the actionof their alkaline salt, their trimethylsilyl derivative or theirdimethylstannyl derivative on the corresponding halogenated precursorcompound, for example according to the following reaction scheme:[CF₃SO₂NSO(C₄H₉)]Cl]+ImSi(CH₃)₃

ClSi(CH₃)₃+[CF₃SO₂NSO(C₄H₉)Im], in which Im represents

[0041] The precursor compounds (Z¹,L), in which the leaving group is apseudohalogen such as a sulfonate, can be obtained by the action of theacid chloride or the anhydride of the sulfonic acid corresponding to thesulfonate, on an abovementioned salt R¹—X¹(Z¹)-Q-X²(O)R²⁻M⁺. Thereaction of a silver salt with a sulfonyl chloride R⁷SO²Cl (R⁷ being ofthe same nature as the groups R^(i)) according to the following schemeis particularly advantageous:

R¹—X(Z¹)-Q-X(O)R²⁻Ag⁺+R⁷SO₂Cl

R¹—X(Z¹)-Q-X(SO₃R⁷)R²+AgCl

[0042] In general, it is advantageous to prepare the precursor compoundsR¹—X¹(Z¹)-Q-X²(L)R from a compound comprising an anion in which thesulfur or the phosphorus are in the oxidation state IV and III,respectively. On oxidizing these anions, the sulfur VI or phosphorus Vderivatives are obtained according to the reaction scheme

R¹—X(Z¹)-Q-X²(R²)⁻A⁺+2L

R¹—X(Z¹)-Q-X²(L)R²+LA

[0043] The preferred compounds for L are halogens, such as fluorine,chlorine or bromine.

[0044] The various leaving groups can be exchanged by techniques thatare well known to those skilled in the art. For example, the chlorinecan be replaced with fluorine by the action of an agent containingactive fluoride ions and an affinity for the chlorine ions, such assilver fluoride AgF or tetramethylammonium fluoride,1,1,1,3,3,3-hexakis(dimethylamino)-diphosphazenium fluoride{[(CH₃)₂N]₃P}₂N⁺F⁻ ortetrakis(tris(dimethylamino)-phosphoranylideneaminophosphonium{[(CH₃)₂N]₃P═N)₄P⁺F⁻, or the compound of addition oftris(dimethylamino)sulfonium fluoride with trimethylfluorosilane[(CH₃)₂N]₃S⁺[Si(CH₃)₃F₂]⁻.

[0045] The imidazole or triazole derivatives can be obtained by theaction of their alkaline salt or their trimethylsilyl or dimethylstannylderivative) on the corresponding derivative, according to the reactionscheme:

[CF₃SO₂NSO(C₄H₉)Cl]+ImSiCH₃)₃

ClSi(CH₃)₃+[CF₃SO₂NSO(C₄H₉)Im]

[0046] in which Im represents imidazolyl, triazolyl or benzotriazolyl.

[0047] A symmetrical compound, in which X¹(Z¹) is identical to X²(Z²),can be prepared by the action of an ionic nitride or a metallicderivative of hexamethyl-disilazane or of ammonia in the presence of abase on a precursor containing a leaving group L, according to thefollowing reaction scheme, in which R, X and Z have the meaning givenabove, respectively, for R^(i), X^(i) and Z^(i), A and L are as definedabove: 2RX(Z)L+A₃N

[RX(Z)]₂N⁻A⁺+2LA. For example:

2CF₃SO(═NSO₂CF₃)F+Li₃N

[CF₃SO(═NSO₂CF₃)]₂N⁻A⁺+2LiF

[0048] The nitriding agent may advantageously be Li₃N, ammonia, itsderivatives with silanes and their alkali metal derivatives such asN[SiCH₃)₃]₂Li, N[SiCH₃)₃]₂Na, and N[SiCH₃)₃]₂K.

[0049] A compound of formula [R¹SO₂N—S★=O(R²)═NSO₂R³]⁻M⁺ can be obtainedby reacting a salt [R¹SO₂NSO₂R²]⁻M′⁺ with a halogenating agent, to givethe precursor R¹SO₂NSOR²(X) (X being a halogen). Said precursor is thencondensed with a sulfonamide R³SO₂NH₂ in the presence of a base or withits metallic derivatives such as R³SO₂NLi₂ or R³SO₂NNa₂. The desiredcation for the final compound is obtained by standard ion-exchangeprocesses.

[0050] In the same way, the ionic carbides allow the compounds[RX(Z)]₃C⁻A⁺ to be prepared, according to the reaction scheme2RX(Z)L+A₄C

[RX(Z)]₃C⁻A+3LA.

[0051] Given the large possible choice for the substituents which can bepresent on the anionic group, the compounds of the invention make itpossible to induce ionic conduction properties in most organic, liquidor polymeric media containing polarity, even low polarity. Theapplications are important in the field of electrochemistry, inparticular for the storage of energy in primary or secondary generators,in supercapacitors, in fuel cells and in electroluminescent diodes. Thecompatibility of the ionic compounds of the invention with organicliquids or polymers makes it possible to induce pronounced antistaticproperties, even when the content of ionic compound is extremely low.Accordingly, another subject of the present invention consists of an ionconducting material consisting of an ionic compound of the presentinvention dissolved in a solvent.

[0052] The ionic compound used to produce an ion conducting material ispreferably chosen from compounds whose cation is ammonium, or a cationderived from a metal, in particular lithium or potassium, zinc, calcium,rare-earth metals, or an organic cation, such as a substituted ammonium,an imidazolium, a triazolium, a pyridinium or a4-dimethylaminopyridinium, said cations optionally bearing a substituenton the carbon atoms of the ring. The ion conducting material thusobtained has high conductivity and high solubility in solvents, onaccount of the weak interactions between the positive charge and thenegative charge. It has a broad field of electrochemical stability, andit is stable in both reducing and oxidizing media. Furthermore, thecompounds which have an organic cation and a melting point below 150°C., in particular the compounds containing an imidazolium, triazolium,pyridinium or 4-dimethylaminopyridinium cation, have high intrinsicconductivity, even in the absence of solvent, when they are in themolten state.

[0053] The solvent for an ion conducting material of the invention canbe an aprotic liquid solvent, a solvating polymer, a polar polymer or amixture thereof. The aprotic liquid solvent is chosen, for example, fromlinear ethers and cyclic ethers, esters, nitriles, nitro derivatives,amides, sulfones, sulfolanes, alkylsulfamides and partially hydrogenatedhydrocarbons. The solvents which are particularly preferred are diethylether, dimethoxyethane, glyme, tetrahydrofuran, dioxane,dimethyltetrahydrofuran, methyl or ethyl formate, propylene or ethylenecarbonate, alkylcarbonates (in particular dimethylcarbonate,diethylcarbonate and methyl propyl carbonate), butyrolactones,acetonitrile, benzonitrile, nitromethane, nitrobenzene,dimethylformamide, diethylformamide, N-methylpyrrolidone, dimethylsulfone, tetramethylene sulfone, tetramethylene sulfone andtetraalkylsulfonamides containing from 5 to 10 carbon atoms.

[0054] The solvent for the ion conducting material can be a polarpolymer chosen from solvating, crosslinked or non-crosslinked polymers,bearing or not bearing grafted ionic groups. A solvating polymer is apolymer which contains solvating units containing at least one heteroatom chosen from sulfur, oxygen, nitrogen and fluorine. As examples ofsolvating polymers, mention may be made of polyethers of linear, comb orblock structure, forming or not forming a network, based onpoly(ethylene oxide), or polymers containing the ethylene oxide orpropylene oxide or allyl glycidyl ether unit, polyphosphazenes,crosslinked networks based on polyethylene glycol crosslinked withisocyanates or networks obtained by polycondensation and bearing groupswhich allow the incorporation of crosslinkable groups. Mention may alsobe made of block copolymers in which certain blocks bear functions whichhave redox properties. Needless to say, the above list is not limiting,and any polymer with solvating properties can be used.

[0055] An ion conducting material of the present invention cansimultaneously comprise an aprotic liquid solvent chosen from theaprotic liquid solvents mentioned above and a polar polymeric solventcomprising units containing at least one hetero atom chosen from sulfur,nitrogen, oxygen and fluorine. It can comprise, from 2 to 98% of liquidsolvent. As examples of such a polar polymer, mention may be made ofpolymers mainly containing units derived from acrylonitrile, fromvinylidene fluoride, from N-vinylpyrrolidone or from methylmethacrylate. These polymers can bear ionic groups. The proportion ofaprotic liquid in the solvent can range from 2% (corresponding to aplasticized solvent) to 98% (corresponding to a gelled solvent). An ionconducting material of the present invention can also contain a saltconventionally used in the prior art for the production of an ionconducting material. Among the salts which can be used as a mixture withan ionic compound according to the invention, the salt most particularlypreferred is chosen from perfluoroalkane sulfonates,bis(perfluoroalkylsulfonyl)imides, bis(perfluoro-alkylsulfonyl)methanesand tris(perfluoroalkyl-sulfonyl)methanes.

[0056] Needless to say, an ion conducting material of the invention canalso contain the additives conventionally used in this type of material,and in particular inorganic or organic fillers in powder or fibre form.

[0057] An ion conducting material of the invention can be used as anelectrolyte in an electrochemical generator. Another subject of thepresent invention is thus an electrochemical generator comprising anegative electrode and a positive electrode which are separated by anelectrolyte, characterized in that the electrolyte is an ion conductingmaterial as defined above. Preferably, the cation of the ionic compoundof the electrolyte is Li⁺ or K⁺. According to one specific embodiment,such a generator comprises a negative electrode consisting of lithiummetal, or an alloy thereof, optionally in the form of a manometricdispersion in lithium oxide, or a nitride double salt of lithium and ofa transition metal, or an oxide of low potential having the generalformula Li_(1+y)Ti_(2−x/4)O₄ (0≦x, y≦1), or carbon and carbon-basedproducts derived from the pyrolysis of organic materials. When thenegative electrode functions by exchanging lithium ions, it isparticularly advantageous to use, for the electrolyte, a compound of theinvention in which the cation is an Li⁺ ion. According to anotherembodiment, the generator comprises a positive electrode chosen fromvanadium oxides VO_(x)(2≦x≦2.5), LiV₃O₈, Li_(y)Ni_(1−x)Co_(x)O₂, (0≦x,y≦1), magnesium spinels Li_(y)Mn_(1−x)M_(x)O₂, (M═Cr, Al, V, Ni,0≦x≦0.5; 0≦y≦2), organic polydisulfides, FeS, FeS₂, iron sulfateFe₂(SO₄)₃, iron and lithium phosphates and phosphosilicates of olivinestructure, or their products of substitution of the iron with manganese,which are used alone or as mixtures. The positive electrode collector ispreferably made of aluminium.

[0058] An ionic compound of the present invention can also be used toinduce an ionic conductivity in media of low polarity, such as aliphaticand aromatic hydrocarbons and media which contain a large fractionthereof, polymers of relatively unpolar and/or hydrophobic nature, andsupercritical carbon dioxide.

[0059] An ion conducting material of the present invention can also beused in a supercapacitor. Another subject of the present invention is,consequently, a supercapacitor using at least one carbon electrode witha high specific surface, or an electrode containing redox polymer, inwhich the electrolyte is an ion conducting material as defined above.

[0060] The ionic compounds of the present invention can be used fordoping polymers in order to improve their electron conduction. Thepolymers concerned are essentially polyacetylenes, polyphenylenes,polypyrrols, polythiophenes, polyanilines and polyquinolines which aresubstituted or unsubstituted, as well as polymers in which the aromaticunits are separated by the vinylene unit —CH═CH—. The doping processconsists in partially oxidizing the polymer in order to createcarbocations whose charge is compensated by the anions in the compoundsof the invention. This doping can be carried, out chemically orelectrochemically, optionally simultaneously with the formation of thepolymer. For this specific application, compounds of the inventionbearing a highly delocalized charge are preferably chosen, in particularthe compounds in which Z is ═C(C≡N)₂ ═NSO₂R or ═C(SO₂R)₂, which impartthermal and mechanical stability properties. The polymers thus doped areanother subject of the present invention.

[0061] In addition, an ion conducting material of the present inventioncan be used as an electrolyte in an electrochromic device. Anelectrochromic device in which the electrolyte is an ion conductingmaterial according to the invention is another subject of the presentinvention. Such a device also comprises electrodes whose active materialis chosen from WO₃, MoO₃, iridium oxyhydroxides IrO_(x)H_(y), (2≦x≦3;0≦y≦3), Prussian blue, viologens and their polymers, and aromaticpolyimides.

[0062] The compounds of the present invention can be used for thecatalysis of various types of chemical reaction, and in particular forpolymerization reactions, condensation reactions, addition orelimination reactions, oxidation or reduction reactions, solvolyses,Friedel-Crafts reactions and Diels-Alder reactions. For theseapplications in catalysis, the compounds will be chosen essentially as afunction of the cation associated with the anionic part.

[0063] For the catalysis of Diels-Alder reactions or Friedel-Craftsreactions, the cations of an alkali metal, of an alkaline-earth metal,of a transition metal or of a rare-earth metal are suitable. Compoundscontaining an H⁺, Li⁺, Mg⁺⁺, Ca⁺⁺, Cu⁺⁺, Zn⁺⁺, Al⁺⁺⁺, Fe⁺⁺⁺ or Fe⁺⁺⁺cation are preferred.

[0064] The compounds of the invention in which the cation is an onium ofthe diazonium, sulfonium, iodonium or metallocenium type can be used ascationic polymerization initiators, in particular for polymerizing orcrosslinking vinyl ethers, epoxides, acetals and cyclic ethers,vinylamides, oxazolines, isobutylene, styrene or siloxanes. Under theaction of actinic radiation, such compounds generate the correspondingacidic form which is capable of initiating a cationic polymerizationreaction. A compound of the invention can be used as a photoinitiatoroptionally in the presence of a sensitizer, or of a radical initiatorwhich can be initiated thermally or by actinic radiation. The compoundsof the invention in the form of an amine salt can serve as initiatorsfor cationic polymerizations by heating to release the correspondingprotonic form. Similarly, if the cation is a salt of a cationic azocompound (for example as represented below), it can serve, by heating,as an initiator for radical polymerizations.

[0065] The present invention makes it possible to obtain compounds inwhich the anion has intrinsic chirality, which makes it possible toinduce enantiomeric asymmetry during the use of said compounds ascatalysts, to prepare stereoregular polymers and to give the materialscontaining them an optical rotation.

[0066] The present invention is explained in further detail by means ofthe examples which follow, which describe the preparation and varioususes of compounds of the invention. However, the invention is notlimited to these examples.

EXAMPLE 1

[0067] The compound of sulfur in the state IV [CF₃SO₂NS(O)CF₃]⁻Na⁺ wasprepared according to one or other of the two possible reaction schemes:

CF₃S—SCF₃+CF₃SO₂NCl₂

CF₃SO₂NS(Cl)CF₃+CF₃SCl   a)

CF₃SO₂NS(Cl)CF₃+NaOS(CH₃)₃

[CF₃SO₂NS(O)CF₃]⁻Na⁺+ClSi(CH₃)₃

[0068] or

CF₃SO₂NNa₂+CF₃SO₂Cl

[CF₃SO₂NS(O)CF₃]⁻Na⁺+NaCl   b)

[0069] The halogenated compound CF₃SO₂NS(Cl)CF₃ was prepared bychloridation of the sodium salt [obtained via one of the routes a) orb)] in the absence of solvent and converted into the fluoro derivativeby the action of N(CH₃)₄F in ether at −35° C.

[0070] 2.67 g of the halogenated compound CF₃SO₂NS(F)CF₃ in 20 ml of THFwere reacted with 170 mg of lithium nitride to give the salt:

EXAMPLE 2

[0071] 15.6 g of butanesulfonyl chloride were dissolved in 100 ml ofanhydrous acetonitrile to which were added 14.9 g oftrifluoromethanesulfonamide and 20.4 g of 1,4-diazabicyclo-2,2,2-octane(DABCO). The mixture was stirred for 4 hours at room temperature and theDABCO hydrochloride formed was then removed by centrifugation and thesolvent was evaporated off. The solid residue was taken up in 100 ml ofa saturated solution of KCl in water to which were added 15 ml of aceticacid. The precipitate of [C₄H₉SO₂NSO₂CF₃]⁻K⁺ was filtered off andpurified by crystallization from hot water.

[0072] 9.22 g of the salt obtained above were dissolved in 50 ml ofanhydrous acetonitrile, to which were added 2.6 ml of oxalyl chloride(COCl)₂ and three drops of DMF acting as catalyst. After the evolutionof gas ceased, 4.4 g of trifluoromethanesulfonamide and 6.73 g of DABCOwere added. After stirring at room temperature, the DABCO hydrochlorideformed was removed by centrifugation and the solution was poured into100 ml of water containing 15% by weight of KCl and 15 ml of aceticacid. The precipitate was separated out, washed with water andrecrystallized from ethanol. It corresponds to the formula:

[0073] The reaction scheme for the successive steps of the process is asfollows:

[C₄H₉SO₂NSO₂CF₃]⁻K⁺+(COCl)₂

KCl+C₄H₉SO(Cl)NSO₂CF₃

C₄H₉SO(Cl)NSO₂CF₃+2N(C₂H₄)₃N

N(C₂H₄)₃NHCl+[C₄H₉SO(NSO₂CF₃)NSO₂CF₃]⁻N(C₂H₄)₃NH⁺

[C₄H₉SO(NSO₂CF₃)NSO₂CF₃]⁻N(C₂H₄)₃NH⁺+KCl

N(C₂H₄)₃NHCl++[C₄H₉SO(NSO₂CF₃)NSO₂CF₃]⁻K⁺,

EXAMPLE 3

[0074] 5 g of the salt of Example 2 were treated with 1.17 g of lithiumtetrafluoroborate in isopropanol. The KBF₄ precipitate was filtered offand the lithium salt was obtained by evaporation of the solvent anddrying under vacuum at 60° C.

[0075] 1 g of polyethylene oxide of mass 10⁶ was dissolved in 30 ml ofacetonitrile with 834 mg of the lithium salt. The solution wasevaporated in a PTFE ring so as to form a 200 μm film. This film isamorphous according to the differential calorimetry study, and has aconductivity of greater than 2.10⁻⁵ Scm⁻¹ at 25° C.

EXAMPLE 4

[0076] 6 ml of a 10M solution of butyllithium in hexane were added to8.97 g of nonafluorobutanesulfonamide in 25 ml of ether at −25° C.,followed by addition of 4.13 g ofbis(trifluoromethyl)trichlorophophorane P(CF₃)Cl₃. The lithium chloridewas removed by filtration and the salt:

[0077] was purified by recrystallization from dioxane and treatment ofthe solvate under vacuum at 80° C. This salt is soluble in relativelynon-polar solvents such as ethyl carbonate (dielectric constant of 2.8)to form a solution which has a conductivity of greater than 4.10⁻³ Scm⁻¹and an anodic oxidation stability of +5.5 V vs. Li°:Li⁺.

EXAMPLE 5

[0078] The compound [C₈H₁₇SO₂NSO₂CF₃]⁻K⁺ was prepared by a proceduresimilar to that of Example 2, using octanesulfonyl chloride. 36.3 g ofthis compound were dissolved in anhydrous DMF and 13 g of(chloromethylene)dimethylammonium chloride [CH(Cl)═N(CH₃)₂]⁺Cl⁻ wereadded. A precipitate of KCl was formed and was removed by filtration.1.7 g of lithium nitride were added to the solution. After stirring for24 hours at room temperature, the reaction product was centrifuged andthe supernatant was poured into 200 ml of water saturated with potassiumchloride. The pasty precipitate was separated out after settling hadtaken place and was washed several times with water and then extractedwith 50 ml of an equivalent-volume mixture of diethoxy-2-ethane anddichloromethane. After evaporation of the solvent, a hydrophobic saltwas obtained, having the formula:

[0079] This compound, either in the initial form of the potassium salt,or in the form of the lithium salt obtained by ion-exchange, haspronounced surfactant and lubricant properties, and it is soluble insolvents with a low dielectric constant, in particular in aromatichydrocarbons. In these two forms, Li or K salt, the compound facilitatesthe extrusion of homo- and copolymers based on ethylene oxide for thepreparation of ion conducting films, as well as for the preparation ofcomposite electrodes in which the active material is an insertioncompound which can be used for the manufacture of electrochemicalgenerators.

EXAMPLE 6

[0080] 253 g of polyaniline protonated in chloride form were suspendedin acetonitrile and 6.7 g of the compound of Example 5 were added. Themixture was stirred for 24 hours and the polymer, in which the chlorideions were exchanged with the ion (CF₃SO₂NSOC₈H₁₇)₂N⁻, was washed withwater and with ethanol to remove the KCl, then dried. The conjugatepolymer in conductive doped form is soluble in solvents of low polaritysuch as xylenes, dichloroethane or chloroform. The conductivity of thepolymer is greater than 1 Scm⁻¹ and stable with respect to atmosphericagents, in particular moisture.

[0081] It has anticorrosion properties. It especially allows ferrousmetals to be protected against corrosion.

EXAMPLE 7

[0082] The ionic compound [CF₃SO₂NSO₂(3,5-C₆H₃(CF₃)₂]⁻K⁺ was prepared bya method similar to that of Example 2, starting with3,5-bis(trifluoromethyl)benzenesulfonyl chloride andtrifluoromethanesulfonamide. 18.6 g of salt were treated with 7 g ofDAST (C₂H₅)₂NSF₃. The fluoro compound obtained:

[0083] was purified by distillation under vacuum. 4.27 g of thiscompound were added to 30 ml of anhydrous THF containing 670 mg ofmalonotrile and 18 mg of lithium hydride. At the end of the reaction,observed by the end of the release of hydrogen, the reaction mixture wasfiltered and the THF was evaporated off. The solid residue was taken upin water and filtered off. 4.4 g of brucine sulfate in 50 ml of waterwere added and the reaction mixture was stirred for 24 hours. Afterseparation and drying, 8 g of the precipitate formed were treated with asolution of 1.6 g of a solution of sodium tetraphenylborate in 20 ml ofan equivalent-volume, water/ethanol solution. After filtration, thesolution was dried to give the sodium salt of the anion, which isintrinsically chiral at its sulfur atom, resolved into an active isomerwith brucine:

[0084] The lithium, magnesium or rare-earth metal and yttrium salts ofthis anion induce enantiomeric excesses of from 50 to 92% during thecatalysis of Diels-Alder reactions and aldol condensations. Acationic-polymerization catalyst was prepared by the action of acetylchloride in stoichiometric amount on the silver salt, which was itselfobtained by exchanging the sodium salt with silver toluene sulfonate inan isopropanol/toluene mixture. This catalyst induces a polymerizationof propylene oxide into an optically active polymer. In a similarmanner, methyl vinyl ether is polymerized into a water-insolublecrystalline isotactic macromolecule, in contrast with the polymersobtained with non-chiral cationic initiators. The compounds:

[0085] also have intrinsic chirality at the anionic centre, allowing thecatalysis of reactions favouring an enantiomer, the polymerizationsgiving polymers which are optically active or which exhibit tacticity.

EXAMPLE 8

[0086] The compound [(C₄H₉SO₂)₂N]Na was prepared according to the methodof Runge et al. (Chem. Ber. 88-4, 533 (1955)) and halogenated withthionyl chloride in acetonitrile, the reaction being catalyzed by DMF.The chloride C₄H₉SO₂NSO(Cl)C₄H₉ dissolved in THF was treated withammonia so as to form the sulfimidosulfamide C₄H₉SO₂NSO(NH₂)C₄H₉.Equimolar amounts of the chloride and the amide were reacted in pyridineto form the pyridinium salt:

[0087] The salt of the rhodamine dye 6G of this anion was precipitatedby simple mixing in water of rhodamine 6G perchlorate and of thepyridinium salt. This salt has pronounced solubility in a large numberof organic solvents, in particular in monomers such as methylmethacrylate or (styrene, and this solubility is maintained during thepolymerization of these monomers. The solid solutions thus formed arehighly fluorescent and allow the preparation of solid lasers, as thinfilms or as fibres.

EXAMPLE 9

[0088] Bis(indenyl)zirconium dichloride was treated with the silver saltof the compound of Example 6 to give the compound:

[0089] in which X⁻ is [CF₃SO₂NSOC₈H₁₇]₂N⁻.

[0090] This metallocene has excellent solubility in the usualpolymerization solvents such as toluene or aliphatic hydrocarbons, andit shows appreciable activity for the polymerization of α-olefins, inparticular for ethylene and propylene.

EXAMPLE 10

[0091] 0.14 g (4.12 mmol) of Li₃N and 0.04 g (0.33 mol) of4-dimethylaminopyridine as catalyst were added, under argon, to asolution of 2.43 g, (8.25 mmol) ofN-(trifluoromethylsulfonyl)phenylsulfonimidoyl fluoride preparedaccording to the method described by Garlyauskajte et al. (Tetrahedron,vol. 50, p. 6891, 1994) in 4 ml of anhydrous THF. The reaction mediumwas then refluxed for 24 hours. After cooling and evaporation of thesolvent under vacuum, the residue obtained was dissolved in 10 ml ofwater and the solution was filtered and then passed through an AmberliteIR-120 ion-exchange column (acidic form). 50% of potassium hydroxidesolution was added to this solution. The precipitate formed wasseparated out, recrystallized from water and then dried by azeotropicdistillation with benzene. The compound below was thus obtained:

[0092] The corresponding lithium salt was obtained by ionic exchangewith lithium chloride in THF. Concentrated solutions of this lithiumsalt in ether are activated for the catalysis of Diels-Alder reactions.

EXAMPLE 11

[0093] 2.83 g (10 mmol) ofN-(trifluoromethyl-sulfonyl)trifluoromethylsulfonimidoyl fluoride,prepared according to the method described in Example 1, dissolved in 4ml of anhydrous THF were added to a solution of 174 mg of Li₃N (10 mmol)in 4 ml of anhydrous THF, followed by addition of 0.04 g (0.33 mmol) of4-dimethylaminopyridine as catalyst. The reaction mixture was thenstirred for 24 hours. After evaporation of the solvents under vacuum,the residue obtained was taken up in saturated KCl solution. Theprecipitate formed was separated out, recrystallized from water and thendried by azeotropic distillation with benzene. The compound below wasthus obtained:

[0094] According to the same process, starting with[C₄F₉SO₂NSOC₄F₉]⁻Na⁺, the compound below was obtained:

EXAMPLE 12

[0095] 22.44 g (200 mmol) of 1,4-diazabicyclo[2.2.2]octane (DABCO)dissolved in 20 ml of anhydrous tetrahydrofuran at 0° C. were added to asolution, at 0° C. and under argon, of 14.36 g (100 mmol) of sulfamoylchloride (CH₃)₂NSO₂Cl (sold by Aldrich) and 14.91 g oftrifluoromethanesulfonamide CF₃SO₂NH₂(100 mmol), prepared according tothe procedure of Example 2, in 60 ml of anhydrous tetrahydrofuran. After2 hours at 0° C., the reaction was continued for 24 hours at roomtemperature. The DABCO hydrochloride precipitate was removed byfiltration on a sinter funnel of porosity No. 4. After evaporation ofthe tetrahydrofuran and drying, the product was dissolved in 25 ml ofethanol. 9.81 g (100 mmol) of potassium acetate CH₃COOK were then addedand the precipitate obtained was then recrystallized from refluxingethanol. After cooling, filtration and drying, the potassium salt(CH₃)₂NSO₂NKSO₂CF₃ was recovered. 50 mmol of this salt were dissolved in30 ml of THF and then treated with 50 mmol of oxalyl chloride. Aprecipitate of potassium chloride formed rapidly, and was removed byfiltration. 5 mmol of Li₃N were then added, under argon, to the(CH₃)₂NS(Cl)O═NSO₂CF₃ solution. After stirring for 72 hours, the solventwas evaporated off and the residue was recrystallized from a solutionsaturated with potassium chloride. The compound below was obtained:

[0096] According to the same process, the compound below was obtained byreplacing the sulfamoyl chloride with butanesulfonyl chloride:

EXAMPLE 13

[0097] 20 mmol of the sodium salt of sulfonimide [(CH₃)₂NSO₂]₂NNa weretreated with 20 mmol of thionyl chloride SOCl₂ in 10 ml of anhydrousacetonitrile. A precipitate of sodium chloride formed rapidly,concomitantly with formation of (CH₃)₂NSO(Cl)═NSO₂N (CH₃)₂. Afterstirring for one hour, 20 mmol of CF₃SO₂NNa₂, prepared beforehand bytreating trifluoromethanesulfonamide with sodium methoxide in methanol,were added under argon. After, stirring for 24 hours, the reactionmedium was filtered and the solvent was then evaporated off. Afterpassage through a cation-exchange column, the compound below wasobtained:

EXAMPLE 14

[0098] 10 mmol of p-styrenesulfonamide, 0.04 g (0.33 mmol) ofdimethylaminopyridine as catalyst and then 0.1 mmol oftert-butylhydroxyquinone were added, under argon, to 10 mmol ofN-(trifluoromethyl-sulfonyl)trifluorosulfonimidoyl fluoride preparedaccording to the method described in Example 1, dissolved in 10 ml ofanhydrous pyridine. The reaction medium was then stirred for 24 hours at40° C. After evaporation of the pyridine under vacuum, the residueobtained was taken up in THF and then stirred for 24 hours in thepresence of an excess of potassium phosphate K₃PO₄. After filtration andevaporation of the solvent, the compound below was obtained:

EXAMPLE 15

[0099] According to a process similar to that of Example 14, andreplacing the p-styrenesulfonamide with allylsulfonamide, the compoundbelow was obtained:

EXAMPLE 16

[0100] 5 mmol of diphenyliodonium chloride (C₆H₅)₂ICl and 5 mmol of thepotassium salt [C₄H₉SO₂N═S(═O)(CF₃)]₂NK described in Example 12 werestirred together for 24 hours in water. By extracting the aqueous phasewith dichloromethane, and after evaporation of the dichloromethane anddrying, the compound below was recovered:

[0101] This salt makes it possible to initiate, under the effect ofactinic radiation (light, γ-rays, electron beams), cationicpolymerization reactions or cationic crosslinking reactions ofelectron-rich monomers, in particular vinyl ethers, propenyl ethers,epoxides, isobutylene or N-vinylpyrrolidinone.

[0102] It is soluble in most common organic solvents (tetrahydrofuran,acetonitrile, dimethylformamide, ethyl acetate, glymes, toluene, etc.)and in aprotic solvating polymers such as polyethylene oxide. It is alsosoluble to more than 10% by weight in reactive solvents such astriethylene glycol divinyl ether or cyclohexanedimethanol divinyl ether,in contrast, for example, with the bis(trifluoromethanesulfonyl)imidesalt of diphenyliodonium.

[0103] The photoinitiating properties of this salt were tested byirradiating a solution of triethylene glycol divinyl ether, containingit at 1% by weight, with U.V. radiation at 254 nm, with a power of 1900mW/cm². After irradiation for a few seconds, the reactive solvent set toa solid, this reaction being highly exothermic.

EXAMPLE 17

[0104] The allylsulfonimide of Example 15 was epoxidized by themagnesium salt of commercial peroxyphthalic acid to give the salt:

[0105] A solution of 100 ml of anhydrous tetrahydrofuran, 50 mmol ofsaid salt and 6 mmol of allyl glycidyl ether were introduced into aParr®-type chemical reactor. After purging the reactor with argon, 146mmol of ethylene oxide and then 100 μl of a 10⁻² M solution of potassiumt-butoxide in THF were introduced using a valve. The polymerization wasthen carried out under argon by heating the reaction medium at 60° C.for 48 hours. After cooling, the solution was concentrated and thepolymer was then recovered by reprecipitation from ether. Afterfiltration and drying, the potassium cations of this polyelectrolytewere exchanged with lithium cations by passage through a cation-exchangecolumn. The polyelectrolyte below was thus obtained:

[0106] x:y:z being for example 6:50:200 on account of the higherreactivity of ethylene oxide. This polymer makes it possible to preparepolymeric electrolytes or gelled electrolytes containing fixed anions,the polymer fulfilling the double function of a matrix for obtaining thegel and of a polyelectrolyte.

[0107] A gelled electrolyte 40 μm in thickness containing (by weight)30% of the above polyelectrolyte, 35% of ethylene carbonate and 35% ofpropylene carbonate) was thus prepared, after crosslinking the allylfunctions by UV irradiation in the presence of1,2-diphenyl-1-keto-2,2-dimethoxyethane. This gel has good mechanicalproperties and a conductivity of greater than 10⁻³ S.cm⁻¹ at 30° C. Thecation-transport number in this electrolyte was estimated at 0.85.

[0108] An electrochemical generator was assembled using, as electrolyte,the gelled electrolyte described above. The anode material was a carboncoke (80% by volume) mixed with the copolymer (PANSDTFSI) of thisexample in non-crosslinked form as binder (20% by volume). The cathodematerial was a composite material consisting of carbon black (6% byvolume), LiCoNiO₂ (75% by volume) and non-crosslinked copolymer(PANSDTFSI) (20% by volume). This generator gave good cyclingperformance at 25° C. It was possible to achieve 1000 charge/dischargecycles between 3 and 4.2 V, preserving a capacitance of greater than 80%of the capacitance at the first cycle. The generator has very goodperformance during a power demand on account of the use of fixed anions.The use of fixed anions also made it possible to improve the change inthe interface resistance.

[0109] This family of polymers is of great practical interest for thedevelopment of electrochemical generators.

EXAMPLE 18

[0110] By ion-exchange in acetone between the potassium salt[C₄H₉SO₂N═S(═O)(CF₃)]₂NK described in Example 12 with3,3′-diethylthiatricarbocyanine iodide (which is an infrared dye of thecyanine family, sold by Aldrich), followed by a reprecipitation fromwater, and after filtration and drying, the compound below was obtained:

[0111] This salt is very soluble in relatively non-polar solvents suchas dichloromethane or methylene chloride, as well as in relativelynon-polar polymer matrices, such as polymethyl methacrylate.

[0112] Moreover, a very pronounced decrease was observed in theaggregation of the cationic dyes with each other on account of the“plasticizing” nature of the di-2-ethylhexylamino groups. This decreasein aggregation is an advantage since the aggregation phenomenon entailsa broadening of the optical absorption bands which can prejudice theoperating accuracy of systems using dyes, in particular optical datastorage disks.

EXAMPLE 19

[0113] 100 mmol of trimethoxysilane were dissolved in tetrahydrofuran ina three-necked round-bottomed flask equipped with a condenser, amechanical stirrer and an inlet for neutral gas (Argon); 100 mmol of thepotassium salt described in Example 15 and 70 mg of chloroplatinic acidH₂PtCl₆ were then added. The mixture was refluxed for 4 hours. Aftercooling and evaporation of the THF, the compound below was obtained:

[0114] This compound was grafted to the surface of silica particlespretreated in hydrochloric acid solution. Such silica particles areparticularly useful for carrying out supported catalysis using asuitable cation.

EXAMPLE 20

[0115] 10 mmol of the potassium salt [C₄F₉SO₂N═S(═O)(CF₃)]₂NK describedin Example 11, were treated with silver tetrafluoroborate in an 80/20mixture of toluene dioxane. After stirring for a few hours, the reactionmedium was filtered to remove the potassium tetrafluoroborateprecipitate and anhydrous hydrogen chloride gas in toluene was thenbubbled through. After filtration to remove the silver chloride formed,and addition of silica particles, the solvent was evaporated off to givethe acid [C₄F₉SO₂N═S(═O)(CF₃)]₂NH deposited on silica. 1 mol of octaneand 10 mmol of acid supported on silica were introduced into a Parrreactor and the reactor was then maintained at 200° C for 10 min. Theoctane was then isomerized into isooctane.

[0116] The acid [C₄F₉SO₂N═S(═O)(CF₃)]₂NH deposited on silica and used asisomerization catalyst has an excellent level of use and is easy torecover on account of its low volatility and its oleophobic nature, i.e.its insolubility in aliphatic hydrocarbons.

[0117] The acid [C₄F₉SO₂N═S(═O)(CF₃)]₂NH dissolved in fluorinatedsolvents such as Fluorinert® (sold by the company 3M) can also be usedto carry out chemical reactions involving an acidic catalysis in atwo-phase medium, the reaction products, which are insoluble in thefluorinated fluid, being recovered by simple separation after settlinghas taken place.

EXAMPLE 21

[0118] 10 mmol of the potassium salt [C₄H₉SO₂N═S(═O)(CF₃)]₂NK, obtainedin Example 12, were stirred in water in the presence of 11 mmol of1-ethyl-3-methyl-1H-imidazolium chloride (10% excess, sold by Aldrich).A liquid phase denser than water was obtained. This phase was recoveredby extraction with dichloromethane. After evaporation of thedichloromethane and drying of the liquid obtained under vacuum at 40°C., the molten salt below was recovered:

[0119] This molten salt has a conductivity of greater than 4.10⁻³ S.cm⁻¹and a freezing point of less than −20° C. Its broad redox stabilityrange makes it a particularly advantageous electrolyte forelectrochemical generators such as lithium batteries, supercapacitors,light modulation systems and photovoltaic cells.

EXAMPLE 22

[0120] 10 mmol of the potassium salt [(CH₃)₂NSO₂N═S(═O)(CF₃)]₂NK,prepared as in Example 12, were dissolved in 20 ml of THF and weretreated with 10 mmol of oxalyl chloride. A precipitate of potassiumchloride formed rapidly and was removed by filtration. 5 mmol of Li₃Nwere then added, under argon, to the filtered solution. After stirringfor 48 hours, the solvent was evaporated off and the residue wasrecrystallized from saturated potassium chloride solution. The compoundbelow was obtained:

1. Ionic compound corresponding to the formula

in which: M^(m+) is a proton or a metal cation having the valency m,chosen from ions of alkali metals, of alkaline-earth metals, oftransition metals or of rare-earth metals, or an organic onium cation oran organometallic cation, 1≦m≦3; X¹ and X², denoted below by X^(i),represent, independently of each other, S=Z³, S=Z⁴, P—R³ or P—R⁴; Qrepresents N, CR⁵, CCN or CSO₂R⁵; Z¹, Z², Z³ and Z⁴, denoted below byZ^(i), represent, independently of each other, ═O, ═NC≡N, ═C(C═N)₂,═NS(=Z)₂R⁶ or ═C[S(=Z)₂R⁶]₂, Z having the same meaning as Z^(i), itbeing understood that, in a segment —X-Q-X²—, not more than 3 groupsZ^(i) represent ═O; R¹, R², R³, R⁴, R⁵ and R⁶, denoted below by R^(i),represent, independently of each other, Y, YO—, YS—, Y₂N— or F; Yrepresents a monovalent organic radical, preferably containing from 1 to16 carbon atoms, chosen from alkyl, alkenyl, oxaalkyl, oxaalkenyl,azaalkyl, azaalkenyl, aryl, alkylaryl or perfluoroalkyl radicals, orfrom the radicals obtained from the abovementioned radicals bysubstitution, in the chains and/or the aromatic part, with hetero atomssuch as halogens, oxygen, nitrogen, sulfur or phosphorus; it beingunderstood that sulfur or phosphorus are present, they can optionally belinked to substituted nitrogen or oxygen atoms, or alternatively Y is arepeating unit of a polymeric frame.
 2. Ionic compound according toclaim 1, characterized in that the cation M^(m+) is a metal cationchosen from K⁺, Li⁺, Mg⁺⁺, Ca⁺⁺ or Ba⁺⁺, Cu⁺⁺, Zn⁺⁺, Fe⁺⁺ or Re⁺⁺⁺. 3.Ionic compound according to, claim 1, characterized in that the cationM^(m+) is an onium cation chosen from the group consisting of ammoniumions, guanidinium ions, amidinium ions, pyridinium ions, imidazoliumions, imidazolinium ions, triazolium ions, sulfonium ions, iodoniumions, phosphonium ions, nitrosyl and NO₂+.
 4. Ionic compound accordingto claim 1, characterized in that the cation M^(m+) is an organometalliccation chosen from metallocenium ions, metal cations coordinated byatoms such as O, S, Se, N, P or As and borne by organic molecules,trialkylsilyl, tetraalkylgermanyl and dialkylstannyl groups in which thealkyl radicals contain from 1 to 10 carbon atoms.
 5. Ionic compoundaccording to claim 4, characterized in that the organometallic cationforms part of a polymer chain.
 6. Ionic compound according to claim 1,characterized in that the cation M⁺ is the repeating unit of a conjugatepolymer in cationic oxidized form.
 7. Ionic compound according to claim1, characterized in that at least one of the groups Xi represents aphosphorous group.
 8. Ionic compound according to claim 7, characterizedin that it corresponds to one of the formulae


9. Ionic compound according to claim 8, characterized in that Qrepresents N.
 10. Ionic compound according to claim 1, characterized inthat the groups X^(i) represent a group S-Z^(i).
 11. Ionic compoundaccording to claim 10, characterized in that Q represents N, it beingunderstood that if R¹ is CF₃, R₂ is a phenyl optionally bearing ahalogen or an NO₂, three substituents Z^(i) represent O and onesubstituent Z^(i) represents. ═NSO₂CF₃, then M is other than an alkalimetal cation or a proton.
 12. Ionic compound according to claim 1,characterized in that the radicals R¹ and R² are chosen, independentlyof each other, from perfluoroalkyl radicals, alkyl radicals, alkenylradicals, dialkylamino radicals and styrenyl radicals.
 13. Ioniccompound according to claim 12, characterized in that the perfluoroalkylradicals contain from 1 to 8 carbon atoms, the alkyl radicals containfrom 1 to 8 carbon atoms, the alkenyl radicals contain from 2 to 18carbon atoms and the alkyl radicals of the dialkylamino groups containfrom 1 to 18 carbon atoms.
 14. Ionic compound according to claim 12,characterized in that at least two groups Z^(i) represent ═O, the groupsZ^(i) different from ═O being ═NSO₂R_(F), R_(F) being a perfluoroalkylgroup.
 15. Ionic compound according to claim 1, characterized in thatthe groups Z^(i) represent, independently of each other, ═CO, ═N—C≡N or═C(C≡N)₂.
 16. Ionic compound according to claim 1, characterized in thatZ¹ to Z³ represent ═O and Z⁴ represents ═C[S (=Z)₂R⁶]₂.
 17. Ioniccompound according to claim 1, characterized in that they correspond toone of the formulae

in which R′⁶ has the same meaning as R⁶ and R_(f) and R′_(f) represent aperfluoroalkyl radical.
 18. Ionic compound according to claim 1,characterized in that it corresponds to the formula[R¹SO₂N—S★═O(R²)═NSO₂R⁶]⁻ in which R¹ is different from R⁶.
 19. Ioniccompound according to claim 1, characterized in that it corresponds tothe formula [R¹SO₂N—S★═O(R²)═N—S★═O(R⁵)═NSO₂R⁶]⁻.
 20. Ionic compoundaccording to claim 19, characterized in that R¹ and R⁶ represent,independently of each other, a radical chosen from F, CF₃, C₂F₅, C₄F₉,C₆F₁₃ and C₈F₁₇, and R² and R⁵ represent, independently of each other,an alkyl, an aryl, an alkylaryl or a dialkylamino preferably containingfrom 1 to 20 carbon atoms.
 21. Process for preparing a compoundaccording to claim 1, characterized in that it consists in reacting acompound R1-X1(Z1)-Q-X2(L)R2 with a compound A2Z2, in which: A is analkali metal, a proton, an amino or phosphorus-containing base, atrialkylsilyl group, a dialkylstannyl group, LiH, MgCl, Li, MgL1, ZnL1,CdL1, Cu, Mg, Zn, Cd, Hg or a trialkylsilyl, trialkylgermanyl ortrialkylstannyl group,. L and L1 are leaving groups.
 22. Process forpreparing a compound according to claim 1, characterized in that itconsists in reacting a compound R¹—X¹(Z¹)-QA2 with a compound L-X²(Z²)R²in which: A is an alkali metal, a proton, an amino orphosphorus-containing base, a trialkylsilyl group, a dialkylstannylgroup, LiH, Li, MgL1, ZnL1, CdL1, Cu, Mg, Zn, Cd, Hg or a trialkylsilyl,trialkylgermanyl or trialkylstannyl group, L and L1 are leaving groups.23. Process according to either of claims 21 and 22, characterized inthat the leaving groups are chosen from halogens, pseudohalogens(including fluorinated or non-fluorinated sulfonates, and imidazoyl,triazolyl and benzotriazole radicals.
 25. Process for preparing acompound according to claim 1, in which X¹(Z¹) is identical to X²(Z²),characterized in that it consists in reacting an ionic nitride or ametallic derivative of hexamethyl-disilazane or of ammonia in thepresence of a base with a precursor containing a leaving group. 26.Process according to claim 25, characterized in that, the nitridingagent is Li₃N, ammonia, its derivatives with silanes and their alkalimetal derivatives such as N[SiCH₃)₃]₂Li, N[SiCH₃)₃]₂Na and N(SiCH₃)₃]₂K.27. Process for preparing a compound according to claim 18,characterized in that it consists in reacting a salt [R₁SO₂N═NSO₂R₂]⁻M′⁺with a halogenating agent, to give the precursor R₁SO₂N═NSOR₂X (X beinga halogen), and then in condensing said precursor with a sulfonamideR₃SO₂NH₂ in the presence of a base, or with a metallic derivative ofsulfonamide such as R₃SO₂NLi₂ or R₃SO₂NNa₂, and in carrying out an ionexchange in order to obtain the desired cation.
 28. Ion conductingmaterial consisting of a solution of an ionic compound according toclaim 1, in a solvent.
 29. Material according to claim 28,,characterized in that the cation of the ionic compound is chosen fromammonium, lithium, potassium, zinc, calcium, a substituted ammonium, animidazolium, a triazolium, a pyridinium and a 4-dimethylaminopyridinium,said cations optionally bearing a substituent on the carbon atoms of thering.
 30. Material according to claim 28, characterized in that thesolvent is an aprotic liquid solvent.
 31. Ion conducting materialaccording to claim 28, characterized in that the solvent is acrosslinked or non-crosslinked solvating polymer, bearing or not bearinggrafted ionic groups.
 32. Ion conducting material according to claim 28,characterized in that the solvent is a mixture of an aprotic liquidsolvent and a polar polymer.
 33. Electrolyte consisting of an ioniccompound dissolved in a solvent, characterized in that the ioniccompound is a compound according to claim
 1. 34. Primary or secondarybattery, comprising a negative electrode, a positive electrode and anelectrolyte, characterized in that the electrolyte contains an ioniccompound according to claim
 1. 35. Primary or secondary battery,comprising a negative electrode, a positive electrode and anelectrolyte, characterized in that the electrolyte is an ion conductingmaterial according to one of claims 30 to
 32. 36. System for modulatinglight, comprising an electrolyte and electrodes, characterized in thatthe electrolyte contains an ionic compound according to claim
 1. 37.Supercapacitor consisting of an electrolyte and electrodes,characterized in that the electrolyte contains an ionic compoundaccording to claim
 1. 38. Process for doping a polymer, which consistsin partially oxidizing said polymer in order to create carbocationswhose charge is compensated by the anions of an ionic compound,characterized in that the ionic compound is a compound according toclaim
 1. 39. Process for polymerizing or crosslinking monomers orprepolymers capable of reacting cationically, characterized in that acompound according to claim 1 is used as a photoinitiating source ofacid for catalyzing the reaction.
 40. Use of an ionic compound accordingto claim 1, as a catalyst for polymerization reactions, for condensationreactions, for addition or elimination reactions, for oxidation orreduction reactions, for solvolyses, for Friedel-Crafts reactions andfor Diels-Alder reactions.
 41. Use of an ionic compound according toeither of claims 18 and 19, for the preparation of optically activeorganic compounds or for enantioselective polymerization reactions.